Oxidation dyeing composition for karatinous fibres and dyeing method using same

ABSTRACT

The invention concerns an oxidation dyeing composition for keratinous fibres, and in particular human keratinous fibres such as hair, comprising, in a medium suited for dyeing, (a) as first coupling agent at least a 3,5-diamino-pyridine derivative suitably selected; (b) and as second coupling agent at least resorcin (1,3-dihydrobenzene) and/or one of its addition salts with an acid; (c) and as third coupling agent at least an oxidation base such as para-phenylenediamine and/or one of its addition salts with an acid. The invention also concerns the dyeing method using said composition.

[0001] The invention relates to a composition for the oxidation dyeingof keratinous fibers, and in particular of human keratinous fibers suchas the hair, comprising, in a medium which is suitable for dyeing,

[0002] as a first coupler, at least one suitably chosen3,5-diaminopyridine derivative;

[0003] and, as a second coupler, at least resorcinol(1,3-dihydroxybenzene) and/or one of its addition salts with an acid;

[0004] and, as a third coupler, at least one meta-aminophenol and/or oneof its addition salts with an acid;

[0005] and at least one oxidation base of the para-phenylenediamine typeand/or one of its addition salts with an acid.

[0006] The invention also relates to the dyeing method using thiscomposition.

[0007] The invention also relates to the dyeing method using thiscomposition.

[0008] It is known practice to dye keratinous fibers, and in particularhuman hair, with dye compositions containing oxidation dye precursors,in particular ortho- or para-phenylenediamines, ortho- orpara-aminophenols and heterocyclic bases which are generally referred toas oxidation bases. Oxidation dye precursors, or oxidation bases, arecolorless or weakly colored compounds which, when combined withoxidizing products, can give rise to colored compounds and dyes by aprocess of oxidative condensation.

[0009] It is also known that the shades obtained with these oxidationbases can be varied by combining them with couplers or color modifiers,the latter being chosen in particular from aromatic meta-diamines,meta-aminophenols, meta-diphenols and certain heterocyclic compounds.

[0010] The variety of molecules used as regards the oxidation bases andthe couplers allows a wide range of colors to be obtained.

[0011] The “permanent” coloration obtained by means of these oxidationdyes must, moreover, satisfy a certain number of requirements. Thus, itmust be able to give shades of the desired intensity and it must be ableto withstand external agents (light, bad weather, washing,permanent-waving, perspiration, rubbing).

[0012] The dyes must also make it possible to cover white hair and,finally, they must be as unselective as possible, i.e. they must givethe smallest possible color differences along the same length ofkeratinous fiber, which may in fact be differently sensitized (i.e.damaged) between its tip and its root.

[0013] Oxidation dyeing compositions containing certain3,5-diaminopyridine derivatives as coupler, in combination withoxidation bases conventionally used in oxidation dyeing, such as, forexample, para-phenylenediamines or para-aminophenols, have already beenproposed, in particular in patents U.S. Pat. No. 4,473,375 and DE 31 32885. Such compositions are not, however, always satisfactory, inparticular from the point of view of the strengths and the chromaticityof the colorations obtained.

[0014] The applicant has now just discovered, completely unexpectedlyand surprisingly, that it is possible to obtain novel dyes that arecapable of giving strong, particularly chromatic and brilliant,relatively unselective colorations which show excellent properties ofresistance to the various attacking factors to which the keratinousfibers may be subjected, by combining a 3,5-diaminopyridine derivativeof formula (I) defined below with resorcinol (1,3-dihydroxybenzene) andwith a third coupler of the meta-aminophenol type and with at least oneoxidation base of the para-phenylenediamine type.

[0015] These discoveries form the basis of the present invention.

[0016] A first subject of the invention is therefore a composition forthe oxidation dyeing of keratinous fibers, and in particular of humankeratinous fibers such as the hair, characterized in that it comprises,in a medium which is suitable for dyeing:

[0017] as a first coupler, at least one 3,5-diamino-pyridine derivativecorresponding to the following general formula (I):

[0018] in which:

[0019] R₁ and R₂, which may be identical or different, represent a C₁-C₄alkyl radical, a C₁-C₄ monohydroxyalkyl radical or aC₂-C₄-polyhydroxyalkyl radical,

[0020] R₃ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical and/or oneof its addition salts with an acid;

[0021] and, as a second coupler, at least resorcinol(1,3-dihydroxybenzene) and/or one of its addition salts with an acid;

[0022] and, as a third coupler, at least one meta-aminophenol and/or oneof its addition salts with an acid;

[0023] and at least one oxidation base of the para-phenylenediamine typeand/or one of their addition salts with an acid.

[0024] The dye composition in accordance with the invention givesstrong, very chromatic colorations which show excellent properties ofwithstanding not only atmospheric agents such as light and bad weather,but also perspiration and the various treatments to which the hair maybe subjected.

[0025] A subject of the invention is also a method for the oxidationdyeing of keratinous fibers using this dye composition.

[0026] Among the 3,5-diaminopyridine derivatives of formula (I) inaccordance with the invention, mention may be made of2,6-dimethoxy-3,5-diaminopyridine, 2,6-diethoxy-3,5-diaminopyridine,2,6-di-(β-hydroxyethyloxy)-3,5-diaminopyridine and their addition saltswith an acid.

[0027] According to the invention, the dye composition preferablycontains 2,6-dimethoxy-3,5-diaminopyridine and/or at least one of itsaddition salts with an acid.

[0028] The 3,5-diaminopyridine derivative(s) of formula (I) which can beused as a first coupler in the dye composition in accordance with theinvention preferably represent(s) from 0.0001 to 10% by weightapproximately of the total weight of the dye composition, and even morepreferentially from 0.005 to 5% by weight approximately of this weight.

[0029] The resorcinol which can be used as a second coupler preferablyrepresents from 0.0001 to 10% by weight approximately of the totalweight of the dye composition, and even more preferentially from 0.005to 5% by weight approximately of this weight.

[0030] Among the meta-aminophenols which are used as a coupler in thedye compositions in accordance with the invention, mention may moreparticularly be made of the following compounds of formula (II) andtheir addition salts with an acid:

[0031] in which:

[0032] R₄ represent a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical;

[0033] R₅ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄alkoxy radical or a halogen atom chosen from chlorine, bromine orfluorine;

[0034] R₆ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄alkoxy radical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄polyhydroxyalkyl radical, a C₁-C₄ monohydroxyalkoxy radical or a C₂-C₄polyhydroxyalkoxy radical.

[0035] Among the meta-aminophenols of formula (II) above, mention maymore particularly be made of meta-aminophenol, 5-amino-2-methoxyphenol,5-amino-2-(β-hydroxyethyloxy)phenol, 5-amino-2-methylphenol,5-N-(β-hydroxyethyl)amino-2-methylphenol,5-N-(β-hydroxyethyl)amino-4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol, 5-amino-4-chloro-2-methylphenol,5-amino-2,4-dimethoxyphenol and 5-(γ-hydroxypropylamino)-2-methylphenol,and their addition salts with an acid.

[0036] The meta-aminophenol(s) which can be used as a third couplerpreferably represent(s) from 0.0001 to 10% by weight approximately ofthe total weight of the dye composition, and even more preferentiallyfrom 0.005 to 5% by weight approximately of this weight.

[0037] Among the para-phenylenediamines which can be used as anoxidation base in the dye composition in accordance with the invention,mention may in particular be made of the following compounds of formula(III) and their addition salts with an acid:

[0038] in which:

[0039] R₇ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ alkyl radical substitutedwith a nitrogenous, phenyl or 4′-aminophenyl group;

[0040] R₈ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ alkyl radical substitutedwith a nitrogenous group;

[0041] R₉ represents a hydrogen atom, a halogen atom such as a chlorine,bromine, iodine or fluorine atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₁-C₄ hydroxyalkoxy radical, anacetylamino(C₁-C₄)alkoxy radical, a C₁-C₄ mesylaminoalkoxy radical or acarbamoylamino (C₁-C₄) alkoxy radical,

[0042] R₁₀ represents a hydrogen or halogen atom or a C₁-C₄ alkylradical.

[0043] Among the nitrogenous groups of formula (III) above, mention mayin particular be made of amino, mono(C₁-C₄)alkylamino,di(C₁-C₄)alkylamino, tri(C₁-C₄)alkylamino, monohydroxy(C₁-C₄)alkylamino,imidazolinium and ammonium radicals.

[0044] Among the para-phenylenediamines of formula (III) above, mentionmay more particularly be made of para-phenylenediamine,para-tolylenediamine, 2-chloro-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N,N-bis(β-hydroxyethyl)-2-methylaniline,4-amino-2-chloro-N,N-bis(β-hydroxyethyl)aniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamineand 2-methyl-1-N-(β-hydroxyethyl)-para-phenylenediamine, and theiraddition salts with an acid.

[0045] Among the para-phenylenediamines of formula (III) above,para-phenylenediamine, para-tolylenediamine,2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine and2-chloro-para-phenylenediamine, and their addition salts with an acid,are most particularly preferred.

[0046] The para-phenylenediamines preferably represent from 0.0005 to12% by weight approximately of the total weight of the dye compositionin accordance with the invention, and even more preferentially from0.005 to 6% by weight approximately of this weight.

[0047] The dye composition in accordance with the invention may alsocontain, in addition to the compound(s) of formula (I) above, toresorcinol and to the meta-aminophenol(s), one or more additionalcouplers which may be chosen from the couplers conventionally used inoxidation dyeing, and among which mention may in particular be made ofsubstituted meta-diphenols, meta-phenylenediamines and heterocycliccouplers such as, for example, indole derivatives, indoline derivatives,pyridine derivatives other than those of the invention and pyrazolones,and their addition salts with an acid.

[0048] These couplers are more particularly chosen from1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene,2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, sesamol, α-naphthol,6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole,6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine,1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one and3-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-methylpyridinium, and theiraddition salts with an acid.

[0049] When they are present, these additional couplers preferablyrepresent from 0.0001 to 10% by weight approximately of the total weightof the dye composition, and even more preferentially from 0.005 to 5% byweight approximately of this weight.

[0050] In addition to the para-phenylenediamines used as oxidationbases, the oxidation dyeing composition in accordance with the inventionmay contain one or more additional oxidation bases which are preferablychosen from the oxidation bases conventionally used in oxidation dyeing,and among which mention may in particular be made ofbisphenylalkylenediamines, para-aminophenols, ortho-aminophenols andheterocyclic bases.

[0051] Among the bisphenylalkylenediamines, mention may moreparticularly be made, by way of example, ofN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)-tetramethylenediamine,N,N′-bis(4-methylaminophenyl)-tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their addition saltswith an acid.

[0052] Among the para-aminophenols, mention may more particularly bemade, by way of example, of para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol,and their addition salts with an acid.

[0053] Among the ortho-aminophenols, mention may more particularly bemade, by way of example, of 2-aminophenol, 2-amino-5-methylphenol,2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their additionsalts with an acid.

[0054] Among the heterocyclic bases, mention may more particularly bemade, by way of example, of pyridine derivatives, pyrimidine derivativesand pyrazole derivatives.

[0055] Among the pyridine derivatives, mention may more particularly bemade of the compounds described, for example, in patents GB 1 026 978and GB 1 153 196, such as 2,5-diaminopyridine,2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine and3,4-diaminopyridine, and their addition salts with an acid.

[0056] Among the pyrimidine derivatives, mention may more particularlybe made of the compounds described, for example, in German patent DE 2359 399 or Japanese patent JP 88-169 571 and JP 91-10659 or patentapplication WO 96/15765, such as 2,4,5,6-tetraamino-pyrimidine,4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

[0057] Among the pyrazole derivatives, mention may more particularly bemade of the compounds described in patents DE 3 843 892 and DE 4 133 957and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE195 43 988, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole,4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethyl-pyrazole,4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole,3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole and4,5-diamino-1-β-hydroxyethylpyrazole, and their addition salts with anacid.

[0058] The additional oxidation base(s) preferably represent(s) from0.0005 to 12% by weight approximately of the total weight of the dyecomposition, and even more preferentially from 0.005 to 6% by weightapproximately of this weight.

[0059] In general, the addition salts with an acid which can be used inthe context of the dye compositions of the invention(pyrazolopyrimidines, compounds of formula (I), additional couplers andoxidation bases) are in particular chosen from hydrochlorides,hydrobromides, sulfates, citrates, succinates, tartrates, lactates andacetates.

[0060] The medium which is suitable for dyeing (or support) generallyconsistsof water or of a mixture of water and at least one organicsolvent in order to solubilize the compounds which would not besufficiently water-soluble. By way of organic solvent, mention may bemade, for example, of C₁-C₄ lower alkanols, such as ethanol andisopropanol; glycerol; glycols and glycol ethers such as2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether,diethylene glycol monoethyl ether and monomethyl ether, and aromaticalcohols such as benzyl alcohol or phenoxyethanol, similar products andmixtures thereof.

[0061] The solvents may be present in proportions preferably of between1 and 40% by weight approximately relative to the total weight of thedye composition, and even more preferentially between 5 and 30% byweight approximately.

[0062] The pH of the dye composition in accordance with the invention isgenerally between 3 and 12 approximately, and preferably between 5 and11 approximately. It may be adjusted to the desired value by means ofacidifying or basifying agents usually used in the dyeing of keratinousfibers.

[0063] Among the acidifying agents, mention may be made, by way ofexample, of inorganic or organic acids such as hydrochloric acid,orthophosphoric acid, sulfuric acid, carboxylic acids such as aceticacid, tartaric acid, citric acid or lactic acid, and sulfonic acids.

[0064] Among the basifying agents, mention may be made, by way ofexample, of aqueous ammonia, alkaline carbonates, alkanolamines such asmono-, di- and triethanolamines, and derivatives thereof, sodiumhydroxide, potassium hydroxide and the compounds of formula (IV) below:

[0065] in which W is a propylene residue optionally substituted with ahydroxyl group or a C₁-C₆ alkyl radical; R₁₁, R₁₂, R₁₃ and R₁₄, whichmay be identical or different, represent a hydrogen atom, a C₁-C₆ alkylradical or a C₁-C₆ hydroxyalkyl radical.

[0066] The oxidation dyeing compositions in accordance with theinvention may also contain at least one direct dye, in particular tomodify the shades or enrich them with glints.

[0067] The dye composition in accordance with the invention may alsocontain various adjuvants conventionally used in compositions for dyeingthe hair, such as anionic, cationic, nonionic, amphoteric orzwitterionic surfactants or mixtures thereof, anionic, cationic,nonionic, amphoteric or zwitterionic polymers or mixtures thereof,inorganic or organic thickeners, antioxidants, penetrating agents,sequestering agents, fragrances, buffers, dispersing agents,conditioners, such as, for example, volatile or nonvolatile silicones,which are modified or unmodified, film-forming agents, ceramides,preserving agents and opacifiers.

[0068] Of course, those skilled in the art will take care to choose thisor these optional additional compound(s) such that the advantageousproperties intrinsically associated with the oxidation dyeingcomposition in accordance with the invention are not, or are notsubstantially, adversely affected by the addition(s) envisioned.

[0069] The dye composition according to the invention may be in variousforms, such as in the form of liquids, of creams or of gels, or in anyother form which is suitable for dyeing keratinous fibers, and inparticular human hair.

[0070] Another subject of the invention is a method for the oxidationdyeing of keratinous fibers, and in particular human keratinous fiberssuch as the hair, using the dye composition as defined above.

[0071] According to this method, at least one dye composition as definedabove is applied to the fibers, the color being developed at acidic,neutral or alkaline pH using an oxidizing agent which is added to thedye composition just at the time of use, or which is present in anoxidizing composition applied simultaneously or sequentially.

[0072] According to a preferred embodiment of the dyeing method of theinvention, the dye composition described above is preferably mixed, atthe time of use, with an oxidizing composition containing, in a mediumwhich is suitable for dyeing, at least one oxidizing agent present in anamount which is sufficient to develop a coloration. The mixture obtainedis then applied to the keratinous fibers and is left to stand on themfor approximately 3 to 50 minutes, preferably approximately 5 to 30minutes, after which the fibers are rinsed, washed with shampoo, rinsedagain and dried.

[0073] The oxidizing agent may be chosen from the oxidizing agentsconventionally used for the oxidation dyeing of keratinous fibers, andamong which mention may be made of hydrogen peroxide, urea peroxide,alkali metal bromates, persalts such as perborates and persulfates, andenzymes such as peroxidases, laccases, tyrosynases and oxidoreductases,among which mention may in particular be made of pyranose oxidases,glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidasesand uricases.

[0074] The pH of the oxidizing composition containing the oxidizingagent as defined above is such that, after mixing it with the dyecomposition, the pH of the resulting composition applied to thekeratinous fibers preferably ranges between approximately 3 and 12, andeven more preferentially between 5 and 11. It is adjusted to the desiredvalue by means of acidifying or basifying agents usually used in thedyeing of keratinous fibres and as defined above.

[0075] The oxidizing composition as defined above may also containvarious adjuvants conventionally used in compositions for dyeing thehair and as defined above.

[0076] The composition which is finally applied to the keratinous fibersmay be in various forms, such as in the form of liquids, of creams or ofgels, or in any other form which is suitable for dyeing keratinousfibers, and in particular human hair.

[0077] Finally, a subject of the invention is a multicompartment deviceor dyeing “kit” or any other multicompartment packaging system, a firstcompartment of which contains the dye composition as defined above and asecond compartment of which contains the oxidizing composition asdefined above. These devices may be equipped with a means for applyingthe desired mixture to the hair, such as the devices described in patentFR-2 586 913 in the name of the applicant.

[0078] The examples which follow are intended to illustrate theinvention without, however, limiting the scope thereof. DYEING EXAMPLES1 2 3 2,6-Dimethoxy-3,5-diaminopyridine 0.242 0.484 0.242dihydrochloride (coupler of formula (I)) Resorcinol 0.11  0.055 0.11 Meta-aminophenol —  0.0545 2-Methyl-5-aminophenol — — 0.369(meta-aminophenol coupler) 2-Methyl-5-N-(2- 0.668 — — hydroxyethyl)aminophenol (meta-aminophenol coupler) Para-phenylenediamine — 0.324. —(oxidation base) N,N-bis-β-hydroxyethyl-para- 1.872 — phenylenediaminesulfate (oxidation base) 2-Hydroxyethyl-para- — — 1.125 phenylenediaminedihydrochloride (oxidation base) Common dye support No. 1    1    2   Demineralized water qs 100 g 100 g

Common Dye Support 1

[0079] Oleyl alcohol polyglycerolated with 4 g 2 mol of glycerol Oleylalcohol polyglycerolated with 5.69 g A.M. 4 mol of glycerol (78% A.M.)Oleic acid 3.0 g Oleylamine containing 7 g 2 mol of ethylene oxide, soldunder the trade name Ethomeen 012 by the company Akzo Diethylaminopropyl3 g A.M. laurylaminosuccinamate, sodium salt containing 55% A.M. Oleylalcohol 5 g Oleic acid diethanolamide 12 g Propylene glycol 3.5 g Ethylalcohol 7.0 g Dipropylene glycol 0.5 g Propylene glycol monomethyl ether9 g Sodium metabisulfite as an aqueous 0.455 g A.M. solution containing35% A.M. Arnmonium acetate 0.8 g Antioxidant, sequestering agent q.s.Fragrance, preserving agent q.s. Monoethanolamine q.s. pH 9.8 Dyes x gDemineralized water q.s. 100 g

Common Dye Support 2

[0080] Oleyl alcohol polyglycerolated with 4 g 2 mol of glycerol Oleylalcohol polyglycerolated with 5.69 g A.M. 4 mol of glycerol (78% A.M.)Oleic acid 3.0 g Oleylamine containing 2 mol of ethylene 7 g oxide, soldunder the trade name Ethomeen 012 by the company Akzo Diethylaminopropyl3 g A.M. laurylaminosuccinamate, sodium salt containing 55% A.M. Oleylalcohol 5 g Oleic acid diethanolamide 12 g Propylene glycol 3.5 g Ethylalcohol 7.0 g Dipropylene glycol 0.5 g Propylene glycol monomethyl ether9 g Sodium metabisulfite as an aqueous 0.455 g A.M. solution containing35% A.M. Ammonium acetate 0.8 g Antioxidant, sequestering agent q.s.Fragrance, preserving agent q.s. Aqueous ammonia containing 20% of NH₃10 g Dyes x g Demineralized water q.s. 100 g

METHOD OF APPLICATION

[0081] The composition obtained is mixed, weight for weight, with 20volumes of aqueous hydrogen peroxide, the pH of which is adjusted with aprecise amount of 85% pure orthophosphoric acid (2.5 g/100 g of aqueoushydrogen peroxide) for examples 1 and 2, and at pH=3 for example 3. Themixture is applied to permanent-waved grey hair containing 90% of whitehairs, in a proportion of 28 g per 3 g of hair, for 30 min. The hair isthen rinsed, washed with a standard shampoo and dried.

[0082] The results are given in the table below: EXAMPLE SHADE OBTAINED1 Purplish blue 2 Black 3 Dark gray

1. A composition for the oxidation dyeing of keratinous fibers, and inparticular of human keratinous fibers such as the hair, characterized inthat it comprises, in a medium which is suitable for dyeing: as a firstcoupler, at least one 3,5-diamino-pyridine derivative corresponding tothe following general formula (I):

in which: R₁ and R₂, which may be identical or different, represent aC₁-C₄ alkyl radical, a C₁-C₄ monohydroxyalkyl radical or aC₂-C₄-polyhydroxyalkyl radical, R₃ represents a hydrogen atom, a C₁-C₄alkyl radical, a C₁-C₄ monohydroxyalkyl radical or a C₂-C₄polyhydroxyalkyl radical and/or one of its addition salts with an acid;and, as a second coupler, resorcinol and/or one of its addition saltswith an acid; and, as a third coupler, a meta-aminophenol and/or one ofits addition salts with an acid; and at least one oxidation base of thepara-phenylenediamine type and/or one of its addition salts with anacid.
 2. The composition as claimed in claim 1, characterized in thatthe 3,5-diaminopyridine derivative(s) of formula (I) is (are) chosenfrom 2,6-dimethoxy-3,5-diaminopyridine,2,6-diethoxy-3,5-diaminopyridine,2,6-di(β-hydroxyethyloxy)-3,5-diaminopyridine and their addition saltswith an acid.
 3. The composition as claimed in claim 1, characterized inthat the 3,5-diaminopyridine derivative of formula (I) is2,6-dimethoxy-3,5-diaminopyridine or one of its addition salts with anacid.
 4. The composition as claimed in any one of claims 1 to 3,characterized in that the 3,5-diaminopyridine derivative(s) of formula(I) represent(s) from 0.0001 to 10% by weight approximately of the totalweight of the dye composition.
 5. The composition as claimed in any oneof claims 1 to 4, characterized in that the resorcinol or one of itsaddition salts with an acid represents from 0.0001 to 10% by weightapproximately of the total weight of the dye composition.
 6. Thecomposition as claimed in any one of claims 1 to 5, characterized inthat the meta-aminophenol(s) is (are) chosen from those corresponding tothe following formula (II):

in which: R₄ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical; R₅represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical or a halogen atom chosen from chlorine, bromine or fluorine; R₆represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkylradical, a C₁-C₄ monohydroxyalkoxy radical or a C₂-C₄ polyhydroxyalkoxyradical.
 7. The composition as claimed in claim 6, in which themeta-aminophenol(s) of formula (II) is (are) chosen frommeta-aminophenol, 5-amino-2-methoxyphenol,5-amino-2-(β-hydroxyethyloxy)phenol, 5-amino-2-methylphenol,5-N-(β-hydroxyethyl)amino-2-methylphenol,5-N-(β-hydroxyethyl)amino-4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol, 5-amino-4-chloro-2-methylphenol,5-amino-2,4-dimethoxyphenol and 5-(γ-hydroxypropylamino)-2-methylphenol,and their addition salts with an acid.
 8. The composition as claimed inany one of claims 1 to 7, characterized in that the meta-diphenol(s)represent(s) from 0.0001 to 10% by weight approximately of the totalweight of the dye composition.
 9. The composition as claimed in any oneof claims 1 to 8, characterized in that the para-phenylenediamine(s) is(are) chosen from those corresponding to the following formula (III):

in which: R₇ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ alkyl radical substitutedwith a nitrogenous, phenyl or 4′-aminophenyl group; R₈ represents ahydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ monohydroxyalkyl radical,a C₂-C₄ polyhydroxyalkyl radical, a (C₁-C₄)alkoxy(C₁-C₄)alkyl radical ora C₁-C₄ alkyl radical substituted with a nitrogenous group; R₉represents a hydrogen atom, a halogen atom such as a chlorine, bromine,iodine or fluorine atom, a C₁-C₄ alkyl radical, a C₁-C₄ monohydroxyalkylradical, a C₁-C₄ hydroxyalkoxy radical, an acetylamino(C₁-C₄)alkoxyradical, a C₁-C₄ mesylaminoalkoxy radical or acarbamoylamino(C₁-C₄)alkoxy radical, R₁₀ represents a hydrogen orhalogen atom or a C₁-C₄ alkyl radical, and their addition salts with anacid.
 10. The composition as claimed in claim 9, in which thepara-phenylenediamine(s) is (are) chosen from para-phenylenediamine,para-tolylenediamine, 2-chloro-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N,N-bis(β-hydroxyethyl)-2-methylaniline,4-amino-2-chloro-N,N-bis(β-hydroxyethyl)aniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamineand 2-methyl-1-N-(β-hydroxyethyl)-para-phenylenediamine, and theiraddition salts with an acid.
 11. The composition as claimed in any oneof claims 1 to 10, in which the para-phenylenediamine(s) represent(s)from 0.0005 to 12% by weight approximately of the total weight of thedye composition.
 12. The composition as claimed in any one of claims 1to 11, characterized in that it contains one or more additional couplerswhich are different from the 3,5-diaminopyridine derivatives of formula(I), from resorcinol and from the meta-aminophenols as defined in thepreceding claims.
 13. The composition as claimed in claim 12, in whichthe additional couplers are chosen from substituted meta-diphenols,meta-phenylenediamines and heterocyclic couplers, and their additionsalts with an acid.
 14. The composition as claimed in claim 12 or 13, inwhich the additional couplers represent from 0.0001 to 10% by weightapproximately of the total weight of the dye composition.
 15. Thecomposition as claimed in any one of claims 1 to 14, characterized inthat it contains one or more additional oxidation bases other than thepara-phenylenediamines.
 16. The composition as claimed in claim 15, inwhich the additional oxidation bases are chosen frombisphenylalkylenediamines, para-aminophenols, ortho-aminophenols andheterocyclic bases.
 17. The composition as claimed in claim 15 or 16, inwhich the additional oxidation bases represent from 0.0005 to 12% byweight approximately of the total weight of the dye composition.
 18. Thecomposition as claimed in any one of claims 1 to 17, characterized inthat the addition salts with an acid are chosen from hydrochlorides,hydrobromides, sulfates and tartrates, lactates and acetates.
 19. Amethod for dyeing keratinous fibers, and in particular human keratinousfibers such as the hair, characterized in that at least one dyecomposition as defined in any one of claims 1 to 18 is applied to saidfibers, and in that the color is developed at acidic, neutral oralkaline pH using an oxidizing agent which is added to the dyecomposition just at the time of use, or which is present in an oxidizingcomposition applied simultaneously or sequentially.
 20. The method asclaimed in claim 19, characterized in that the oxidizing agent presentin the oxidizing composition is chosen from hydrogen peroxide, ureaperoxide, alkali metal bromates, persalts such as perborates,percarbonates and persulfates, peracids and enzymes.
 21. Amulticompartment device, or multicompartment dyeing “kit”, a firstcompartment of which contains a dye composition as defined in any one ofclaims 1 to 18 and a second compartment of which contains an oxidizingcomposition.